EP1966296A1 - Masses de moulage a base de polycarbonate - Google Patents

Masses de moulage a base de polycarbonate

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Publication number
EP1966296A1
EP1966296A1 EP06818989A EP06818989A EP1966296A1 EP 1966296 A1 EP1966296 A1 EP 1966296A1 EP 06818989 A EP06818989 A EP 06818989A EP 06818989 A EP06818989 A EP 06818989A EP 1966296 A1 EP1966296 A1 EP 1966296A1
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EP
European Patent Office
Prior art keywords
composition according
weight
modified
polymer
solvent
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EP06818989A
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German (de)
English (en)
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EP1966296B1 (fr
Inventor
Eckhard Wenz
Uwe Peucker
Thomas Eckel
Dieter Wittmann
Arno Nennemann
Vera Buchholz
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Covestro Deutschland AG
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Bayer MaterialScience AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles

Definitions

  • the invention relates to polycarbonate compositions having improved thermal stability and a lower maximum rate of decomposition in case of fire.
  • PC / ABS compositions polycarbonate / acrylmitrile / butadiene / styrene
  • alkylammonium montmorillonites are used, which are preferably distributed in the ABS phase (Wang, S., Hu, Y., Wang, Z, Yong, T, Chen, Z., & Fan, W., Synthesis and Characterization of polycarbonate / ABS / montmorillonite nanocomposite, Polymer Degradation and Stabihty, 80, no. 1, (2003) 157-61).
  • Iron ions decompose the polycarbonate Mat ⁇ x and increase, for example, the heat release rate (determined by Cone Calo ⁇ met ⁇ e) (Stretz, H.A., Koo, J.H., Dimas, V. M, &
  • the heat release rate (cone calometre) was reduced and a longer time to ignition was found, i. the LOI (Limiting oxygen index) was higher and the fire behavior of the samples was rated in the UL94 V test with the classification V-O.
  • WO 99/43747 A1 discloses the synergistic effect for the flameproofing properties of alkylammonium montmorillonites for PC / ABS compositions and teaches that the time to ignition of PC / ABS compositions is prolonged by the addition of the alkylammonium Montm ⁇ llomtes Clayton HY becomes
  • US 2005/0137287 A1 discloses polycarbonate compositions containing sheet silicates modified with a block copolymer of 2- (dimethylamino) styrene-ethyl methacrylate having a quaternary ammonium head group.
  • the resulting polycarbonate molding compositions are transparent and show no discoloration.
  • nanocomposite materials consist of block or graft copolymers and a layered hate, the copolymer bearing a structural unit compatible with the layered hate cat and another unit compatible with the polymer matrix.
  • the described composite materials are prepared in a first step by mixing layered hate with copolymer at elevated temperature and in a subsequent step by extrusion in the desired polymer matrix. Alternatively, a solvent may also be added. It is achieved as an improvement in the tensile strength of the modified material. Not described are PC / ABS compositions and modification processes of the phyllosilicates via the aqueous route.
  • the object underlying the invention is then to provide polycarbonate molding compositions having a high thermal stability, a low maximum decomposition rate after ignition and a low smoke density.
  • compositions according to the invention are distinguished by the fact that no long-chain quaternary ammonium salts are used as stabilizers and a reduction in the molecular weight of the polycarbonate is avoided, which also results in a high mechanical property level of the molding compositions according to the invention.
  • the present invention therefore relates to compositions or thermoplastic molding compositions containing
  • thermoplastic homo- and / or copolymer optionally a thermoplastic homo- and / or copolymer
  • compositions of the invention contain
  • E 0 to 30 parts by weight, preferably 1 to 20 parts by weight, in particular 4 to 15 parts by weight Phosphorverbmdung.
  • All weights M in the present application are normalized such that the sum of the parts by weight of the components A + B + C + D + E m of the composition is normalized to 100.
  • Aromatic polycarbonates and / or aromatic polyester carbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for example, see Schnell, Chemistry and Physics of Polycarbonates, Interscience Pubhshers, 1964, and DE-AS 1 495 626, DE -A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396, for the preparation of aromatic polyester carbonates, eg DE-A 3 077 934) ,
  • Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)
  • A is a single bond, C 1 to C 5 alkylene, C 2 to C 5 alkynes, C 5 to C 6 cycloalkyhdene, -O-, -SO-, -CO-, -S-, -SO 2 -, C to C-arylene, to which further aromatic rings containing optionally heteroatoms may be condensed,
  • B is in each case C 1 to C 4 -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine,
  • x each independently 0, 1 or 2
  • n is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X 1 , R 5 and R 6 are simultaneously alkyl.
  • Preferred diphenols are hydrochon, resorcm, dihydroxydiphenols, bis (hydroxyphenyl) -C -alkanes, bis (hydroxyphenyl) -C-C-cycloalkanes, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfoxides , Bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) -sulfones and ⁇ , ⁇ -bis (hydroxyphenyl) -ds-propylbenzenes and their ring-brominated and / or ring-chlorinated derivatives.
  • diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 1, 1 - Bis (4-hydroxyphenyl) -3,3,5-t-methylcyclohexane, 4,4'-dihydroxydiphenylsulfido, 4,4'-dihydroxydiphenylsulfone and their di- and tetrabrominated or chlorinated derivatives, for example 2,2-bis (3-chloro-4-) hydroxyphenyl) -propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) -propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane.
  • 2,2-bis (4-hydroxyphenyl) propane bisphenol-A
  • the diphenols can be used individually or as any mixtures.
  • the diphenols can
  • Chain terminators suitable for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- [2- (2,4,4 -T ⁇ rnethylpentyl)] - phenol, 4- (l, 3-tetramethyl-butyl) -phenol according to DE-A 2,842,005 or monoalkylphenol or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-tert.
  • alkylphenols such as 4- [2- (2,4,4 -T ⁇ rnethylpentyl)] - phenol, 4- (l, 3-tetramethyl-butyl) -phenol according to DE-A 2,842,005 or monoalkylphenol or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl
  • the amount of chain terminators to be used is generally between 0.5 mol%, and 10 mol%, based on the molar sum of the diphenols used in each case.
  • the thermoplastic, aromatic polycarbonates have weight average molecular weights (M w , measured, for example, by ultracentrifuge or scatter gauge) of from 10,000 to 200,000 g / mol, preferably from 15,000 to 80,000 g / mol, particularly preferably from 24,000 to 32,000 g / mol.
  • thermoplastic, aromatic polycarbonates may be branched in a known manner, preferably by the formation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those containing three and more phenolic groups.
  • both homopolycarbonates and copolycarbonates are suitable.
  • inventive copolycarbonates according to component A it is also possible to use 1 to 25% by weight, preferably 2.5 to 25% by weight, based on the total amount of diphenols to be used, of hydroxyaryloxy endblocked polydiorganosiloxanes. These are known (US 3 419 634) and can be prepared by literature methods. The preparation of polydiorganosiloxane-containing copolycarbonates is described in DE-A 3 334 782.
  • Preferred polycarbonates in addition to the bisphenol A homopolycarbonates, are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sums of diphenols, of other than preferred or particularly preferred diphenols, in particular 2,2-bis (3,5 dibromo-4-hydroxyphenyl) -propane.
  • Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphtha-2,6-dicarboxylic acid. Particular preference is given to mixtures of the diacid dichlorides of isophthalic acid and of terephthalic acid in a ratio of between 1:20 and 20: 1
  • a carbonyl halide preferably phosgene, is additionally used as the bifunctional acid derivative.
  • the amount of chain terminators is in each case from 0.1 to 10 mol%, based in the case of the phenolic chain terminators on moles of diphenol and in the case of monocarboxylic acid chloride terminators on moles of dicarboxylic acid dichloride.
  • the aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.
  • the aromatic polyester carbonates can be branched both linearly and in a known manner (see DE-A 2 940 024 and DE-A 3 007 934).
  • Suitable branching agents are, for example, trifunctional or polyfunctional carboxylic acid chlorides, such as tetiminic acid, cyanuric acid, 3,3 ', 4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in quantities from 0.01 to 1.0 mole percent (based on dicarboxylic acid dichloride used) or trifunctional or more functional phenols such as phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) hept-2 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-Thn- 4-hydroxyphenyl) ethane, T ⁇ - (4-hydroxyphenyl)
  • the proportion of carbonate structure units can vary as desired.
  • the proportion of carbonate groups is up to 100 Mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups.
  • Both the ester and the carbonate portion of the aromatic polyester carbonates may be present in the form of blocks or randomly distributed in the polycondensate.
  • the relative solution viscosity ( ⁇ re i) of the aromatic polycarbonates and polyester carbonates is in the range of 1.18 to 1.4, preferably 1.20 to 1.35 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride Solution at 25 ° C).
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any desired mixture.
  • Component B comprises one or more graft polymers of
  • the graft base B.2 generally has an average particle size (d 50 value) of 0.05 to 10 .mu.m, preferably 0.1 to 5 .mu.m, particularly preferably 0.2 to 1 .mu.m.
  • Monomers B.l are preferably mixtures of
  • B 1.1 50 to 99 parts by weight of vinylaromatics and / or ring-substituted vinylaromatics (such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C r C 8 ) -alkyl esters, such as methyl methacrylate, Ethyl methacrylate), and
  • B.1.2 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C 1 -C 8 ) -alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate , and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.
  • vinyl cyanides unsaturated nitriles such as acrylonitrile and methacrylonitrile
  • acrylic acid (C 1 -C 8 ) -alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate , and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-pheny
  • Preferred grafting bases B.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers (for example according to B1 and B.1.2), with the proviso that the glass transition temperature of the component B.2 below ⁇ 10 0 C, preferably ⁇ 0 0 C, particularly preferably ⁇ -10 0 C hues.
  • Especially preferred is pure polybutadiene rubber.
  • the gel content of the graft base B.2 is at least 30 wt .-%, preferably at least 40% by weight (measured in toluene).
  • the graft copolymer B are prepared by radical polymerization, for example by emulsion, suspension, solution or mass polymerization, preferably by emulsion or mass polymerization.
  • Particularly suitable graft rubbers are also ABS polymers which are prepared in the emulsion polymerization process by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
  • Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of alkyl acrylates, optionally with up to 40 wt .-%, based on B.2 other polymerizable, ethylemsch unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include C
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least three ethylenically unsaturated groups.
  • Particularly preferred crosslinking monomers are the Cychian monomers T ⁇ allylcyanurat, T ⁇ allylisocyanurat, T ⁇ acryloyl- hexahydro-s-t ⁇ azin, T ⁇ allylbenzole.
  • the amount of crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the graft B.2.
  • cychschen crosslinking monomers having at least three ethylenically unsaturated groups it is advantageous to limit the amount to less than 1 wt .-% of the graft B.2.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used in addition to the acrylic acid esters for the preparation of the graft B 2 are, for example Acrylnit ⁇ l, styrene, ⁇ -methylstyrene, acrylamides, vinyl-C, -C 6 -alkyl ethers, methyl methacrylate, butadiene , Preferred acrylate rubbers as the graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • Suitable graft bases according to B.2 are silicone rubbers with graft-active sites, as described in DE-OS 3,704,657, DE-OS 3,704,655, DE-OS 3 631 540 and DE-OS 3 631 539
  • the average particle size d 50 is the diameter, above and below which each 50 wt .-% of the particles are. It can be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).
  • Component C comprises one or more thermoplastic vinyl (Co) polymers Cl and / or polyalkylene terephthalates C.2.
  • Suitable vinyl (Co) polymers are polymers of at least one monomer from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C 1 -C 8 ) -alkyl esters, unsaturated carboxylic acids and also derivatives (such as anhydrides and Imides) unsaturated carboxylic acids. Particularly suitable are (co) polyme ⁇ sates
  • the vinyl (co) polyme ⁇ sate Cl are resinous, thermoplastic and rubber-free. Particularly preferred is the Copolyme ⁇ sat of C 1.1 styrene and C.1.2 Acrylnit ⁇ l.
  • Preferred polyalkylene terephthalates contain at least 80 wt .-%, preferably at least 90 wt .-%, based on the dicarboxylic acid terephthalate and at least 80 wt .-%, preferably at least 90 mol%, based on the diol component of ethylene glycol and / or butanediol-1 , 4- and / or 1,3-propanediol radicals.
  • the preferred polyalkylene terephthalates may contain up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms.
  • Contain atoms eg Residues of propanediol-1,3, 2-ethylpropanediol-1,3-neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol-1,4, 3-ethylpentanediol-2,4, 2 Methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3,3-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3-hexanediol-2,5,1,4-di- ( ⁇ -hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (4- ⁇ -hydroxyethoxy -phenyl) -
  • the polyalkylene terephthalates can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, e.g. in accordance with DE-A 1 900 270 and US Pat. No. 3,692,744.
  • preferred branching agents are T ⁇ mesin Textre, T ⁇ mellithklare, T ⁇ methylolethan and -propane and pentaerythritol.
  • polyalkylene terephthalates prepared from terephthalic acid alone and their reactive derivatives (e.g., their dialkyl esters) and ethylene glycol and / or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.
  • Polyalkylene terephthalates contain 1 to 50 wt .-%, preferably 1 to 30 wt .-%, polyethylene terephthalate and 50 to 99 wt .-%, preferably 70 to 99 wt .-%, polybutylene terephthalate.
  • the polyalkylene terephthalates preferably used have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, as measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. in the Ubbelohde viscometer.
  • the polyalkylene terephthalates can be prepared by known methods (see, for example, Kunststoff-Handbuch, Volume VIII, pp. 695 et seq., Carl-Hanser-Verlag, Kunststoff 1973).
  • Vmyl (co) polyme ⁇ sate or polyalkylene terephthalates may be present in amounts of from 0 to 45, preferably 1 to 30 and more preferably 2 to 25 weight points in the inventive composition.
  • Component D
  • Component D comprises layer compounds which are modified by means of a solvent-free melt process with organic polymers.
  • Layer compounds in the invention are preferably layer composites which have a dimension of nanosize, i. less than 100 nm. This dimension is referred to below as the "average thickness" of the layer composite, and those which have an average thickness of from 0.3 to 10 nm, particularly preferably from 0.5 to 10 nm, particularly preferably from 0.7 to 2, are preferably used
  • the layers have a diameter of from 5 to 10000 nm, preferably from 10 to 2000 nm, particularly preferably from 10 to 1000 nm
  • the cation exchange capacitances of the anionic, unmodified layer compounds are between 10 and 260 meq / 100 g.
  • Counterions (ie, cation) of the unmodified layered compounds may be calcium, magnesium, potassium, sodium, lithium ions, preferably sodium or lithium ions
  • These cations may be derived, for example, either from natural (geological) sources, in the commercial minerals or by ion exchange as described by Lagaly (Lagaly, G., reactions of clay minerals. In Tonminerale and Tone, Stemkopff Verla g, Darmstadt, 1993).
  • the dimensions of the layer bonds ie diameter or the average thickness of the layers of the layer compound
  • the determination of the cation exchange capacity can be carried out, for example, according to L.P. Meier and G. Kahr (Clays & Clay Minerals, 1999, 47, 3, pp. 386-388).
  • layer compounds synthetic as well as naturally occurring layer compounds are used for this purpose. Preference is given to layer compounds of the mineral type Montmo ⁇ llomt, Hecto ⁇ t, and the layered silicates or Tonmmerale allevardite, amesite, beidellite, Fluorhecto ⁇ t, Fluorvermicuht, mica, Halloysit, Hecto ⁇ t, Ilht, Montmo ⁇ llonit, muscovite, nontronite, PaIy- gorskit, saponite, Sepioht, smectite, stevensite , Talc, vermiculite, synthetic talc types and the alkahsilicates maghemite, magadnt, kenyaite, makatite, silmaite, grumantite, revdite and their hydrated forms and the associated crystalline silicic acids or other inorganic layer compounds such as hydrotalcites, double hydroxides and heteropolyacids.
  • Silicate-containing layer compounds are particularly preferably used as layer compounds. Particular preference is given to using silicate-containing layered compounds of the mercurial type montmorillonite, as contained as the main constituent in the bentomet, and to hector material which has a cation exchange capacity between 10 and 260 meq / 100 g, an average thickness of 0.3 to 10 nm, especially preferably from 0.5 to 10 nm, particularly preferably from 0.7 to 2 nm, and an average knife of the layers of 5 to 10,000 nm, preferably from 10 to 2000 nm, more preferably from 10 to 1000 nm.
  • the mixture is heated to a temperature above the melting temperature of the polymer or polymer mixture used, preferably with constant mixing, for example by means of an internal kneader or an extruder, and
  • the heated mixture resulting from step (n) may be incorporated as such into the polycarbonate composition of the invention, for example via a side extruder.
  • Polyalkylene oxides are preferably used as organic polymers for this modification. These polyalkylene oxides preferably have a number-average molecular weight of from 106 to 20 000 g / mol, particularly preferably from 200 to 10 000 g / mol, although it is also possible to use mixtures of various polyalkylene oxides.
  • the polyalkylene oxides used are preferably polyethylene oxides and polyethylene oxide-propylene oxide copolymers. Particular preference is given to using linear polyethylene oxides and most preferably poly (ethylene glycol) monomethyl ether.
  • step (i) Polycarbonate (component A) and / or polymethyl methacrylate (PMMA) is preferably used for this purpose.
  • Phosphorus-containing flame retardants (E) in the sense according to the invention are preferably selected from the groups of mono- and oligomeric phosphoric and phosphonic acid esters, phosphonatoamines and phosphazenes, mixtures of several components selected from one or more various of these groups can be used as flame retardants.
  • Other halogen-free phosphorus compounds not specifically mentioned here can also be used alone or in a difficult combination with other halogen-free phosphorus compounds.
  • Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (PV)
  • R 1, R 3 R 3 and R 1 independently of one another, each optionally halogenated C 1 to C 6 alkyl, in each case optionally substituted by alkyl, preferably C 1 to C 4 alkyl, and / or halo, preferably chlorine, bromine, substituted C 5 to C 3 -C 6 cycloalkyl, C 1 -C 20 "aryl or
  • n independent of each other, 0 or 1
  • X is a mono- or polynuclear aromatic radical having 6 to 30 C atoms, or a higher or branched aliphatic radical having 2 to 30 C atoms, which may be OH-substituted and may contain up to 8 ether bonds.
  • R 1, R 2, R 3 and R 4 are independently C ⁇ to C ⁇ alkyl, phenyl, naphthyl or phenyl-C j -C alkyl.
  • the aromatic groups R 1, R 2, R 3 and R 4 may in turn be tuiert substitutable with halogen and / or alkyl groups, preferably chlorine, bromine and / or C j to C ⁇ alkyl.
  • Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brormerten and chlorinated derivatives thereof.
  • X in the formula (IV) is preferably a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms. This is preferably derived from diphenols of the formula (I).
  • n in the formula (PV) may independently be 0 or 1, preferably n is equal to 1.
  • q stands for values from 0 to 30 When using mixtures of different components of the
  • X is particularly preferred for
  • X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol.
  • X is particularly preferably derived from bisphenol A.
  • ohgomeren phosphoric acid esters of the formula (IV), which are derived from bisphenol A is particularly advantageous since the compositions equipped with this phosphorus compound have a particularly highists ⁇ ss- and hydrolysis resistance and a particularly low tendency to deposit formation in the injection molding. Furthermore, a particularly high heat resistance can be achieved with these flame retardants.
  • Monophosphorus compounds of the formula (IV) are in particular T ⁇ butylphosphat, T ⁇ s- (2-chloroethyl) phosphate, T ⁇ s- (2,3-dibromprobyl) phosphate, T ⁇ phenylphosphat, T ⁇ kresylphosphat, Diphenylkresylphosphat, Diphenyloctylphosphat, diphenyl-2-ethyl cresyl phosphate, T ⁇ - (isopropyl - phenyl) -phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methyl diphenyl ester, diethyl Phenylphosphonklad aryl phosphates, dimethyl methylphosphonate, diphenyl methyl diphenyl ester, diethyl Phenylphosphonklad aryl phosphates, dimethyl methylphosphonate, diphenyl methyl diphenyl ester, die
  • the phosphorus compounds according to component E (IV) are known (cf., for example, EP-A 363 608, EP-A 640 655) or can be prepared by known methods in an analogous manner (for example, Ulimanns Enzyklopadie der ischen Chemie, Vol 301 ff., 1979; Houben-Weyl, Methoden der organischen Chemie, Vol. 12/1, p 43; Beilstem, Vol. 6, p. 177).
  • the mean q values can be determined by determining the composition of the phosphate mixture (molecular weight distribution) using a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) and calculating the mean values for q become.
  • Phosphonatamines are preferably compounds of the formula (V)
  • A is a radical of the formula (Va)
  • R ⁇ and Rl2 independently of one another unsubstituted or substituted C] -C () -, are alkyl or unsubstituted or substituted Ci Cg to Q-aryl,
  • Rl3 and d4 are independently of each other unsubstituted or substituted C ] to CI Q-
  • RL3 and R * 4 together represent unsubstituted or substituted C3 to Ci Q alkylene
  • y is the numerical values O, 1 or 2 and
  • B * is independently hydrogen, optionally halogenated C2 to Cg-alkyl, unsubstituted or substituted Cg to C j Q -aryl.
  • B ⁇ is preferably independently hydrogen, ethyl, n- or iso-propyl, which may be substituted by halogen, unsubstituted or C 1 -C 4 -alkyl and / or halogen-substituted C 1 -C 8 -aryl, in particular phenyl or naphthyl ,
  • Ste alkyl in R ⁇ , R ⁇ j R14 R13 unc h t independently preferably methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec. or tert-butyl, pentyl or hexyl.
  • R13 un R14 may be substituted d independently preferably phenyl, naphthyl or binaphthyl, in particular o-phenyl, o-naphthyl, o-binaphthyl, which halogen (generally mono-, di- or trisubstituted).
  • Rl3 and Rl4 can form a ring structure together with the oxygen atoms to which they are directly attached and the phosphorus atom.
  • Phosphazenes are compounds of the formulas (VIa) and (VIb)
  • Each R is the same or different and is amino, in each case optionally halogenated, preferably fluorine-halogenated Q to Cg-alkyl, or Cj to Cg-alkoxy, in each case optionally by alkyl, preferably C ⁇ to C ⁇ alkyl, and / or halogen, preferably Chlorine and / or bromine, substituted C5 to Cg-cycloalkyl, Cg to C20-aryl, preferably phenyl or naphthyl, C ⁇ to C20'Aryloxy, preferably phenoxy, naphthyloxy, or C7 to Ci 2-aralkyl, preferably phenyl-Cj-C ⁇ alkyl, stands,
  • the phosphazenes can be used alone or as a mixture.
  • the radical R may always be the same or 2 or more radicals in the formulas (Ia) and (Ib) may be different.
  • Phosphazenes and their preparation are described for example in EP-A 728 81 1, DE-A 1 961668 and WO 97/40092.
  • the flame retardants can be used alone or in any mixture with each other or in mixture with other flame retardants.
  • the phosphorus-containing flame retardant may be used in an amount of 0.1 to 30, preferably 1 to 25, and most preferably 2 to 20 weight points in the composition of the present invention.
  • the flame retardants according to component E are often used in combination with so-called Antid ⁇ ppingffenn which the tendency of the material for burning dripping in
  • Compositions are used. Fluorinated polyolefins are preferably used as antidropping agents.
  • the fluorinated polyolefins are generally present in the mixture in an amount of from 0.01 to 3, preferably from 0.05 to 1.5, parts by weight.
  • the fluorinated polyolefins can be used as a pre-compound with the graft polymer (component B) or a copolymer, preferably based on styrene / acrylonitrile.
  • the fluorinated polyolefins are mixed as a powder with a powder or granules of the graft polymer or Copolyme ⁇ sats and compounded in the melt generally at temperatures of 200 to 330 0 C in conventional units such as internal mixers, extruders or twin-screw.
  • the fluorinated polyolefins can also be used in the form of a masterbatch, which is prepared by emulsion polymerization of at least one monoethylated unsaturated monomer in the presence of an aqueous dispersion of the fluorinated polyolefin.
  • Preferred monomer components are styrene, acrylmitrile and mixtures thereof.
  • the polymer is used after acid precipitation and subsequent drying as a free-flowing powder.
  • the coagulates, pre-compounds or masterbatches usually have solids contents of fluo ⁇ ertem polyolefin of 5 to 95 wt .-%, preferably 7 to 60% by weight.
  • composition may contain other conventional polymer additives (component G) such as flame retardants, lubricants and mold release agents, for example pentaerythritol tetrastearate, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing agents (for example glass or carbon fibers, mica, kaolm, talc, CaCO 3 and glass flakes ) as well as dyes and pigments.
  • component G such as flame retardants, lubricants and mold release agents, for example pentaerythritol tetrastearate, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing agents (for example glass or carbon fibers, mica, kaolm, talc, CaCO 3 and glass flakes ) as well as dyes and pigments.
  • flame retardants for example pentaerythritol tetrastearate
  • nucleating agents for example pentaerythritol tetrastearate
  • the mixing of the individual constituents can be carried out in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
  • the layer compound by means of a solvent-free melt process with organic polymers, preferably with polyalkylene oxides having a number average molecular weight of 106 to 20,000 g / mol, more preferably from 200 to 10,000 g / mol used, including mixtures of various polyalkylene oxides can be used, modified,
  • the layered compound masterbatch resulting in the first step (i) can be isolated or else directly processed as a melt, preferably with a side extruder, into the molding compound in step (s).
  • oligomers or polymers selected from the group consisting of polycarbonate (according to component A) and polymethyl methacrylate (PMMA) are used.
  • thermoplastic molding compositions according to the invention are suitable for the production of molded articles of any type, in particular those with increased demands on the maximum heat release rates.
  • the molding compositions of the invention can be used for the production of moldings of any kind. These can be produced by injection molding, extrusion and blow molding. Another form of processing is the production of moldings by deep drawing from previously produced plates or films.
  • Another object of the present invention is therefore also the use of the molding compositions according to the invention for the production of moldings of any kind, preferably the above-mentioned, as well as the moldings of the molding compositions according to the invention.
  • Such shaped bodies are films, profiles, housing parts of any kind, eg for domestic appliances such as juice presses, coffee machines, mixers; for office machines such as monitors, flat screens, notebooks, printers, copiers; Panels, pipes, electrical installation ducts, windows, doors and more Profiles for the construction sector (interior and exterior applications) as well as electrical and electronic components such as switches, plugs and sockets and components for commercial vehicles, in particular for the automotive sector.
  • domestic appliances such as juice presses, coffee machines, mixers
  • office machines such as monitors, flat screens, notebooks, printers, copiers
  • the molding compositions according to the invention can also be used, for example, for the production of the following moldings or moldings: interior fittings for rail vehicles, ships, aircraft, buses and other motor vehicles, housings of electrical appliances containing small transformers, housings for information processing and transmission equipment, housings and panels for medical applications Apparatus, massage apparatus and housings therefor, toy vehicles for children, flat wall elements, housings for safety devices, heat-insulated transport containers, fittings for plumbing and bathroom equipment, cover grids for ventilator openings and housings for garden tools.
  • Cationically modified layered hate (modified with stearylbenzyldimethylammonium chloride) (nanofil 9, powder, specific gravity approx. 1.8 g / cm 3 , average particle size 8 ⁇ m, particle size with complete dispersion approx. 100-500 nm x 1 nm, manufacturer: Fa. Süd-Chemie AG).
  • Nanofil 757 (highly pure sodium montmorillonite, powder, specific gravity about 2.6 g / cm 3 , average particle size ⁇ 10 ⁇ m, particle size with complete dispersion about 500 nm x 1 nm, manufacturer Fa. Süd-Chemie AG). The dimensions were determined by TEM recording and XRD measurements: mean layer thickness of 1 nm and layer diameter of about 300-1000 nm.
  • Component Gl pentaerythritol tetrastearate
  • Component G2 Phosphite Stabihsator
  • Component G3 tetraphenylphosphonium phenolate
  • Example 1 represents the comparison without addition of layered silicate
  • Example 2 contains as comparison a commercially available cationically modified layered hate
  • Example 3 contains the above-described layered silicate-polycarbonate masterbatch.
  • the finished granules are processed on an injection molding machine to the corresponding specimens (melt temperature 260 0 C, mold temperature 80 0 C, flow front speed 240 mm / s) and according to ISO 1133 (MVR), ISO 5660-1 (Cone Kalo ⁇ met ⁇ e) and ASTM E 662 (Flue gas density) and characterized by Thermogravimet ⁇ scher analysis (TGA)
  • MVR melt volume flow rate
  • MeIt volume flow rate MeIt volume flow rate
  • the determination of the cone calorimeter measurement (50 kW / m 2 , 60 mm distance) is carried out in accordance with ISO 5660-1.
  • Thermogravimet ⁇ analysis was carried out with a TGA / SDTA 85 Ie (Mettler-Toledo). Approximately 10 mg of the samples were weighed and rinsed under a gas mixture of 20% oxygen in helium at a flow rate of 80 ml / mm 30 mm at 25 ° C and then heated to 800 0 C at a heating rate of 5K / min. During the entire measurement, the weight change was continuously monitored and the mass was recorded in the mass spectrometer. Table 2 shows the temperature range for the decomposition taken from the measured percentage weight loss or weight loss rate (in% mm -1 ) The initial value corresponds to the beginning of the decomposition, the end value to the end of the decomposition.
  • MARHE Maximum Average Rate of Heat Emission

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)
EP06818989A 2005-12-17 2006-12-06 Masses de moulage a base de polycarbonate Not-in-force EP1966296B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005060463A DE102005060463A1 (de) 2005-12-17 2005-12-17 Polycarbonat-Formmassen
PCT/EP2006/011694 WO2007068384A1 (fr) 2005-12-17 2006-12-06 Masses de moulage a base de polycarbonate

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EP1966296A1 true EP1966296A1 (fr) 2008-09-10
EP1966296B1 EP1966296B1 (fr) 2010-06-23

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EP (1) EP1966296B1 (fr)
JP (1) JP5258574B2 (fr)
KR (1) KR101363805B1 (fr)
CN (1) CN101336270B (fr)
AT (1) ATE471962T1 (fr)
BR (1) BRPI0620009A2 (fr)
CA (1) CA2633193C (fr)
DE (2) DE102005060463A1 (fr)
ES (1) ES2346352T3 (fr)
RU (1) RU2442804C2 (fr)
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CN101932612B (zh) * 2008-02-01 2012-11-21 阿科玛股份有限公司 用于耐擦洗性以及湿粘附性的水性乳液聚合物
DE102008062903A1 (de) * 2008-12-23 2010-06-24 Bayer Materialscience Ag Flammgeschützte schlagzähmodifizierte Polycarbonat-Zusammensetzungen
CN101812223A (zh) * 2009-12-25 2010-08-25 上海锦湖日丽塑料有限公司 聚碳酸酯/聚对苯二甲酸乙二醇酯树脂组合物及制备方法
EP2820077B1 (fr) * 2012-02-29 2019-09-18 SABIC Global Technologies B.V. Compositions de copolymère de polycarbonate thermoplastique, procédés pour les fabriquer et leurs utilisations
EP3020752A1 (fr) * 2014-11-17 2016-05-18 LANXESS Deutschland GmbH Semi-produit à matrice de fibres ignifuge
JP2016117810A (ja) * 2014-12-19 2016-06-30 大建工業株式会社 不燃塗料組成物、それを用いた不燃性板材及び耐火性構造
EP3736309A1 (fr) * 2019-05-07 2020-11-11 Trinseo Europe GmbH Composition de polycarbonate présentant une apparence tachetée lorsqu'elle est moulée
CN110330776B (zh) * 2019-06-22 2021-06-29 宁波浙铁大风化工有限公司 一种低温增韧耐候改性的生物基pc材料及其制备方法

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CA2633193A1 (fr) 2007-06-21
ES2346352T3 (es) 2010-10-14
RU2442804C2 (ru) 2012-02-20
RU2008129115A (ru) 2010-01-27
CN101336270A (zh) 2008-12-31
ATE471962T1 (de) 2010-07-15
DE502006007291D1 (de) 2010-08-05
EP1966296B1 (fr) 2010-06-23
JP2009520046A (ja) 2009-05-21
WO2007068384A1 (fr) 2007-06-21
US7868070B2 (en) 2011-01-11
US20070142535A1 (en) 2007-06-21
DE102005060463A1 (de) 2007-06-28
CA2633193C (fr) 2014-03-25
KR101363805B1 (ko) 2014-02-14
KR20080079321A (ko) 2008-08-29
CN101336270B (zh) 2011-08-03
BRPI0620009A2 (pt) 2011-10-25
TW200738804A (en) 2007-10-16
TWI399398B (zh) 2013-06-21

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